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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Preliminary results: Root cause investigation of orbital anomalies and failures in NASA standard 50 ampere-hour nickel-cadmium batteries

Two lots of NASA standard 50 A.H. Ni-Cd battery cells, manufactured by Gates Aerospace Batteries and built into batteries by McDonnell Douglas, have experienced significant performance problems. The two lots were used on the Compton Gamma Ray Observatory and the Upper Atmosphere Research Satellite. Both of these satellites are Low Earth Orbital (LEO) satellites containing batteries on a parallel bus charged to NASA standard V/T curves using a NASA standard power regulator. The following preliminary conclusions were reached: (1) several plate and cell parameters have migrated within their spec limits over the years (in some cases, from one extreme to the other); (2) several parametric relationships, not generally monitored and therefore not under specification control, have also migrated over the years; (3) many of these changes appear to have taken place as a natural consequence of changes in GE/GAB materials and processes; (4) several of these factors may be 'conspiring' to aggravate known cell failure mechanisms (factors such as heavier plate, less teflon and/or less-uniform teflon, and less electrolyte) but all are still in spec (where specs exist); (5) the weight of the evidence collected to characterize the anomalies and to characterize the negative electrode itself, strongly suggests that alterations to the structure, composition, uniformity, and efficiency of the negative electrode are at the heart of the battery performance problems currently being experienced; and (6) further investigation at all levels (plate, cell, battery, and system) continues to be warranted.

Toft, Mark R.↗
DOE OSTI2024

Vacancy-mediated transport and segregation tendencies of solutes in fcc nickel under diffusional creep: A density functional theory study

The Nabarro-Herring (NH) diffusional creep theory postulates the vacancy-mediated transport of atoms under a stress gradient as the creep mechanism under low-stress and high-temperature conditions. In multicomponent alloys, we premise that this stress-assisted flow of vacancies to and from grain boundaries will produce elemental segregation. An observation of such segregation, validated with theoretical predictions, can provide the necessary experimental evidence for the occurrence of NH creep. Theoretical calculations of the segregation tendencies via analyzing the dominant solute diffusion mechanisms and the difference in diffusivities of the elements are therefore essential. To this end, this study applies density functional theory calculations of migration barriers and solute-vacancy binding energies as input to the self-consistent mean-field theory to assess the vacancy-mediated diffusion mechanisms, transport coefficients, and segregation tendencies of Co, Cr, Mo, Re, Ta, and W solutes in face-centered-cubic Ni. We find Co, Re, and W to be slow diffusers at high temperatures and Cr, Mo, and Ta to be fast diffusers. Further analysis shows that the slow diffusers tend to always enrich at vacancy sinks over a wide range of temperatures. In contrast, the fast diffusers show a transition from depletion to enrichment as the temperature lowers. Furthermore, our analysis of the segregation tendencies under tensile hydrostatic strains shows that slow diffusers are largely unaffected by the strain and favor enrichment. On the other hand, the fast diffusers exhibit high sensitivity to strain and their segregation tendency can transition from depletion to enrichment at a given temperature. Finally, the transport coefficients calculated in this work are expected to serve as input to mesoscale microstructure models to provide a more rigorous assessment of solute segregation under NH creep conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Grain boundary velocity and curvature are not correlated in Ni polycrystals

Grain boundary velocity has been believed to be correlated to curvature, and this is an important relationship for modeling how polycrystalline materials coarsen during annealing. We determined the velocities and curvatures of approximately 52,000 grain boundaries in a nickel polycrystal using three-dimensional orientation maps measured by high-energy diffraction microscopy before and after annealing at 800°C. Unexpectedly, the grain boundary velocities and curvatures were uncorrelated. Instead, we found strong correlations between the boundary velocity and the five macroscopic parameters that specify grain boundary crystallography. The sensitivity of the velocity to grain boundary crystallography might be the result of defect-mediated grain boundary migration or the anisotropy of the grain boundary energy. The absence of a correlation between velocity and curvature likely results from the constraints imposed by the grain boundary network and implies the need for a new model for grain boundary migration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Rational synthesis of high-performance Ni-rich layered oxide cathode enabled via probing solid-state lithiation evolution

Lithium (Li)-ion batteries using nickel (Ni)-rich layered oxide cathode have been pursued with interest due to high practical energy density. A fundamental understanding of the reaction pathways and structural evolution of the solid-phase synthesis of these materials is crucial for their rational design and process development for mass production. In this work, structural evolution during solid-state synthesis was traced via in situ technique, with a particular emphasis on the lithiation reaction and migration of transition metal (TM) ions. The sintering process is governed by the competitive relationship of decomposition and lithiation reactions, which can be regulated through temperature windows. Controlling the melting point of the Li sources, as well as their affinity to cathode precursors, is highly desired to maintain the layered ordering of TM ions throughout the whole synthesis process, which simplifies the manufacturing process and improves the quality of the manufactured cathode material.

25 ENERGY STORAGE↗
NASA NTRS2000

Segregation Behavior of Sulfur and Other Impurities Onto the Free Surfaces of ED-Ni Deposits

Most researchers attribute grain boundary embrittlement in electro-deposited Nickel (ED-Ni) to the presence of small quantities of Sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of Sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of Sulfur was intentionally maintained. A new method was developed to study Sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

Panda, Binayak↗
NASA NTRS2001

Segregation Behavior of Sulfur and Other Impurities onto the Free Surfaces of ED-NI Deposits

Most researchers attribute grain boundary embrittlement in electro-deposited nickel (ED-Ni) to the presence of small quantities of sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of sulfur was intentionally maintained. A new method was developed to study sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

Panda, B.↗
DOE OSTI2023

Formation of active sites on transition metals through reaction-driven migration of surface atoms

Adopting low-index single-crystal surfaces as models for metal nanoparticle catalysts has been questioned by the experimental findings of adsorbate-induced formation of subnanometer clusters on several single-crystal surfaces. Here we used density functional theory calculations to elucidate the conditions that lead to cluster formation and show how adatom formation energies enable efficient screening of the conditions required for adsorbate-induced cluster formation. We studied a combination of eight face-centered cubic transition metals and 18 common surface intermediates and identified systems relevant to catalytic reactions, such as carbon monoxide (CO) oxidation and ammonia (NH 3 ) oxidation. We used kinetic Monte Carlo simulations to elucidate the CO-induced cluster formation process on a copper surface. Scanning tunneling microscopy of CO on a nickel (111) surface that contains steps and dislocations points to the structure sensitivity of this phenomenon. Metal-metal bond breaking that leads to the evolution of catalyst structures under realistic reaction conditions occurs much more broadly than previously thought.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Performance of 12Ah aerospace nickel-cadmium cells of design variable groups

The design variable program of NASA is a systematic approach to evaluate the performance of 12Ah aerospace nickel-cadmium cells of 9 important cell designs. These cells were life cycled in a Low-Earth Orbit (LEO) regime for 3 to 4 years. Representative cells taken from the design variable groups after different cycling periods have been examined. The results show that: (1) positive swelling and carbonate content in the electrolyte increases as a function of the number of cycles, (2) electrolyte distribution follows the order NEG greater than POS greater than SEP, 3) control and no PQ groups outperformed the rest of the groups and (4) the polypropylene group shows very heavy cadmium migration and poor performance.

Vasanth, K. L.↗
DOE OSTI2023

Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li 2 MnO 3 ·0.3LiFeO 2 Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies

We report the use of iron 1s3p resonant X-ray emission processes to conduct spin-selective, high-energy resolution fluorescence detected X-ray absorption near-edge spectroscopy (HERFD-XANES) on an iron-containing, lithium- and manganese-rich, fully earth-abundant cathode material, Li 1.3 Mn 0.5 Fe 0.2 O 2 (0.7Li 2 MnO 3 ·0.3LiFeO 2 ). Coupling this technique with conventional Mn K-edge XANES and detailed extended X-ray absorption fine structure (EXAFS) analysis from both the Mn and Fe vantage points, we gain fundamental insights into the redox processes and migration tendencies of transition metals in this cathode material at the bulk level. We show that during the first charge, Fe 3+ undergoes oxidation to form Fe 4+ prior to the activation plateau. Toward the end of activation, a significant fraction of the iron is present as tetrahedral Fe 3+ . This observation reveals that iron migration from octahedral to tetrahedral sites and iron reduction are initiated during activation. Upon first discharge from the activated state, a continuous and overlapping reduction of both Fe and Mn is observed, with Fe largely restored back as an octahedrally coordinated Fe 3+ . The manganese local environment gradually changes to a distorted cooperative Jahn–Teller Mn 3+ structure during discharge, with the clear presence of two Mn–O as well as two Mn–Mn correlation distances at 2.0 V. The significant reduction of manganese in the very first discharge is distinctly different from that seen in typical nickel-based lithium-manganese-rich materials but is similar to that observed for pure Li 2 MnO 3 . In conclusion, these findings shed light on key structure–property correlations in the cathode material and point to a causative relationship between the redox mechanisms as well as structural changes endured by the material and relatively poor performance during extended electrochemical cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Role of Pr-Vacancies and O-Interstitials on the Activity and Stability of (Pr 1−x Ln x ) 2 NiO 4 (Ln = La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) towards Oxygen Reduction Reactions: A DFT Study

Praseodymium nickelate, Pr 2 NiO 4 (PNO), is a promising electrode to promote oxygen reduction reaction (ORR) in a solid oxide fuel cell, but it exhibits phase transformation during electrochemical operation. The origin of the simultaneous phase transformation and high electrochemical performance remains obscure. We carried out a systematic density functional theory study to elucidate the mechanism for this conjugated phenomenon. Charge, electronic structure, and normal-mode analysis suggest the presence of peroxide. Our study shows that the formation of peroxide (O 2 2– ) is attributed to both oxygen interstitials and Pr vacancies. The peroxide species limits the oxygen ion migration due to the additional energy required to break its O–O bond, which leads to a decrease in ORR activity. Subsequently, we investigate the diffusion paths of Pr-ions while comparing them with those of other Ln 3+ ions (La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) in PNO. The formation energies for various Ln 3+ cation occupancies are calculated, as well as segregation energies in CeO 2 (111) surfaces. Lastly, criteria for effective Ln 3+ dopants are developed. La, Nd, and Pm are proposed as potential substituents in PNO to obtain a stable structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Implications of Microstructure in Helium-Implanted Nanocrystalline Metals

Helium bubbles are known to form in nuclear reactor structural components when displacement damage occurs in conjunction with helium exposure and/or transmutation. If left unchecked, bubble production can cause swelling, blistering, and embrittlement, all of which substantially degrade materials and—moreover—diminish mechanical properties. On the mission to produce more robust materials, nanocrystalline (NC) metals show great potential and are postulated to exhibit superior radiation resistance due to their high defect and particle sink densities; however, much is still unknown about the mechanisms of defect evolution in these systems under extreme conditions. Here, the performances of NC nickel (Ni) and iron (Fe) are investigated under helium bombardment via transmission electron microscopy (TEM). Bubble density statistics are measured as a function of grain size in specimens implanted under similar conditions. While the overall trends revealed an increase in bubble density up to saturation in both samples, bubble density in Fe was over 300% greater than in Ni. To interrogate the kinetics of helium diffusion and trapping, a rate theory model is developed that substantiates that helium is more readily captured within grains in helium-vacancy complexes in NC Fe, whereas helium is more prone to traversing the grain matrices and migrating to GBs in NC Ni. Our results suggest that (1) grain boundaries can affect bubble swelling in grain matrices significantly and can have a dominant effect over crystal structure, and (2) an NC-Ni-based material can yield superior resistance to irradiation-induced bubble growth compared to an NC-Fe-based material and exhibits high potential for use in extreme environments where swelling due to He bubble formation is of significant concern.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ab Initio Design of High-Entropy Thermal/ Environmental Barrier Coatings

Next generation thermal/environmental barrier coatings (TEBC) require carefully balancing various properties including phase stability, thermal conductivity, coefficient of thermal expansion (CTE), mechanical properties, and resistance against hot corrosion and water vapor recession. This work mainly focuses on rapid design of cost-effective high entropy rare-earth disilicates and aluminum garnets to protect SiC-based ceramic matrix composites and nickel-based superalloys in the hot section of gas turbine engines using density functional theory methods. Our calculations identify several low-cost high entropy TEBC exhibiting ultralow thermal conductivity at 1500 K and desirable CTE while maintaining good mechanical properties, including Er1/2Y3/4Yb3/4Si2O7, Gd1/4Er1/4Y3/4Yb3/4Si2O7, Eu1/4Er1/4Y3/4Yb3/4Si2O7, and (Y1/4Gd1/4Er1/4Yb1/4)3Al5O12. This work also aims to gain fundamental understanding of oxygen diffusion in model disilicates. Minimizing oxidizer (such as water vapor and oxygen) permeability through the EBC layer can significantly decrease the growth rate of thermally grown oxide and extend the service life of the coating system. Oxygen diffusion mechanisms including formation energy of defects under varying oxygen conditions and defect migration energy barriers will be presented.

coefficient of thermal expansion↗
DOE OSTI2026

Understanding Fundamental Mechanisms Behind Anomalous Segregation Behavior at Grain Boundaries during Diffusional Creep

Recent experimental studies in a nickel (Ni)-rhenium (Re) alloy demonstrated anisotropic elemental segregation around grain boundaries (GBs) while under tensile strain. Some GBs showed Re enrichment, while others showed Re depletion. We hypothesize that differing vacancy fluxes to GBs, caused by the anisotropic elastic stresses generated within the polycrystal, results in anisotropic creep-induced segregation (CIS) and grain growth. Using molecular dynamics simulations, we developed a mechanistic understanding of CIS and determined the contribution of elastic stresses and grain growth in Ni-Re alloys. We find that the stress state of the GB significantly changes the segregation energy profile for Re atoms, leading to significant Re redistribution. Further, as the GB migrates, the segregation/desegregation tendency of Re leads to bands of Re enrichment/depletion. Our results have important consequences for the quantitative predictions of diffusion creep and for the design of high-temperature creep-resistant Ni alloys.

36 - MATERIALS SCIENCE↗
NASA NTRS1986

A study of the microstructure of a rapidly solidified nickel-base superalloy modified with boron

The microstructures of melt-spun superalloy ribbons with variable boron levels have been studied by transmission electron microscopy. The base alloy was of approximate composition Ni-11% Cr-5%Mo-5%Al-4%Ti with boron levels of 0.06, 0.12, and 0.60 percent (all by weight). Thirty micron thick ribbons display an equiaxed chill zone near the wheel contact side which develops into primary dendrite arms in the ribbon center. Secondary dendrite arms are observed near the ribbon free surface. In the higher boron bearing alloys, boride precipitates are observed along grain boundaries. A concerted effort has been made to elucidate true grain shapes by the use of bright field/dark field microscopy. In the low boron alloy, grain shapes are often convex, and grain faces are flat. Boundary faces frequently have large curvature, and grain shapes form concave polygons in the higher boron level alloys. It is proposed that just after solidification, in all of the alloys studied, grain shapes were initially concave and boundaries were wavy. Boundary straightening is presumed to occur on cooling in the low boron alloy. Boundary migration is precluded in the higher boron alloys by fast precipitation of borides at internal interfaces.

Speck, J. S.↗
NASA NTRS1987

Analysis of 12 AH aerospace nickel-cadmium cells from the design variable program

The Design Variable Program of NASA/GSFC provided a systematic approach to evaluate the performance of 12 Ampere-Hour Nickel-Cadmium cells of different designs. Design Variables tested in this program included teflonated negative plates, silver treated negative plates, lightly loaded negative plates, positive plates with no cadmium treatment, plate design of 1968 utilizing old and new processing techniques and electrochemically impregnated positive plates. These cells were life cycled in a Low-Earth Orbit (LEO) regime for 3 to 4 years. Representative cells taken from the Design Variable Program were examined via chemical, electrochemical and surface analyses. The results indicate the following: (1) positive swelling and carbonate content in the electrolyte increase as a function of number of cycles; (2) electrolyte distribution follows a general order NEG greater than POS greater than SEP; (3) control and No PQ groups outperformed the rest of the groups; and (4) the polyproylene group exhibited heavy cadmium migration and poor performance.

Vasanth, Kunigahalli L.↗
DOE OSTI2026

Evaluation of high-temperature properties of binary, eutectic Ni-X alloys (X = B, Ca, Ce, La, Y, Zr)

We investigated the high-temperature behavior of binary eutectic nickel-base alloys with low-solubility elements, towards developing alloys with new combinations of structural and functional (e.g. thermal or corrosion) properties. Based on thermodynamic screening, we cast binary near-eutectic Ni-B, Ni-Ca, Ni-Ce, Ni-La, Ni-Y, and Ni-Zr alloys and characterized their microstructure and high-temperature properties. All alloys (except Ni-Ca) contain a fine eutectic microstructure, containing submicron alternating lamellae of γ-Ni and continuous intermetallic phases. The eutectic microstructure did not significantly coarsen at 700°C (except for Ni-B), but measurably coarsened in all alloys at 900°C, most quickly in Ni-B, followed by Ni-Ce, Ni-La, Ni-Y, and Ni-Zr. Coarsening in these alloys occurs by fault migration; diffusion within the intermetallic, and its interfacial energy, likely influence coarsening kinetics. At room-temperature, all alloys possess negligible ductility due to the continuous, brittle intermetallic. At 700 and 900°C, the Ni-Zr alloy showed the best combination of strength and ductility. Oxidation experiments at 900°C on Ni-Zr and Ni-Ce revealed heavy internal oxidation of the continuous intermetallic phase. Overall, the Ni-Zr alloy showed good high-temperature coarsening resistance and strength, though ductility and oxidation resistance require improvement for use in structural applications. Possible routes for improving alloy properties via additive manufacturing are discussed.

Ekaputra, Clement [ORNL] (ORCID:0000000307166479)↗
DOE OSTI2025

The microscopic mechanisms of high temperature oxidation of Haynes 282

Nickel-based superalloy finds widespread applications in aerospace and extreme environments. They are known for their high temperature oxidation resistance under extended periods. However, the oxide formation and evolution which sets the stages for the later parabolic oxidation kinetics is not fully understood. This paper aims to provide new insights into the transient stage oxidation mechanism and kinetics of a typical Ni-based superalloy (Haynes 282). While tracking the chemical and microstructural evolution under micrometer scale at 800°C, we show that the oxide scale and its grain boundary species change significantly during the initial stages of oxidation and can have a profound impact on the oxidation kinetics. Cr 2 O 3 forms initially at the grain boundary along with minor amount of Al 2 O 3 . Then, the grain boundary region is enriched with copious amounts TiO 2 while Cr migrates away from the grain boundary. A noticeable change in the isothermal oxidation kinetics observed likely results from a mechanistic change from uniform surface oxidation to preferential outward diffusion of Ti 4+ ions through the grain boundary. Through first-principles calculations combined with energy dispersive spectroscopy, we confirmed the preferential outward diffusion of Ti 4+ ions as the diffusion barrier is lower for Ti than Cr along the grain boundaries. In conclusion, these findings highlight the critical role of early-stage grain boundary oxidation dynamics in dictating the long-term oxidation resistance of Ni-based superalloys and provide a foundation for future strategies to enhance their performance in extreme environments.

DFT↗
NASA NTRS2000

An Interconnected Network of Core-Forming Melts Produced by Shear Deformation

The formation mechanism of terrestrial planetary is still poorly understood, and has been the subject of numerous experimental studies. Several mechanisms have been proposed by which metal-mainly iron with some nickel-could have been extracted from a silicate mantle to form the core. Most recent models involve gravitational sinking of molten metal or metal sulphide through a partially or fully molten mantle that is often referred to as a'magma ocean. Alternative models invoke percolation of molten metal along an interconnected network (that is, porous flow) through a solid silicate matrix. But experimental studies performed at high pressures have shown that, under hydrostatic conditions, these melts do not form an interconnected network, leading to the widespread assumption that formation of metallic cores requires a magma ocean. In contrast, here we present experiments which demonstrate that shear deformation to large strains can interconnect a significant fraction of initially isolated pockets of metal and metal sulphide melts in a solid matrix of polycrystalline olivine. Therefore, in a dynamic (nonhydrostatic) environment, percolation remains a viable mechanism for the segregation and migration of core-forming melts in a solid silicate mantle.

Bruhn, D.↗